Methine dyes with large organic counter anion for dye sensitized solar cells

An electrode layer comprising a porous film made of oxide semiconductor fine particles sensitized with a dye of formula (I),

• where
• n is 1, 2, 3, 4, 5 or 6;
• R1 and R2 are independently of each other selected from hydrogen, unsubstituted C1-C20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, substituted C1-C20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, unsubstituted C1-C20-cycloalkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, substituted C1-C20-cycloalkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, unsubstituted C6-C20-aryl, substituted C6-C20-aryl, unsubstituted C6-C20-heteroaryl, substituted C6-C20-heteroaryl;
• or
• R1 can additionally be a residue of formula D;
• each D is independently selected from the group consisting of residues of formulae D.1 and D.2
• where
• * denotes the bond to the remaining compound of formula (I);
• R17 and R18 are independently of each other selected from unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, where R14 is hydrogen, C1-C20-alkyl or C6-C10-aryl;
• or
• R17 and R18 form together with the nitrogen atom to which they are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• or
• R17 and R20 form together with the nitrogen atom to which R17 is attached and the carbon atoms of the benzene ring to which R20 and N—R17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• or
• R17 and R22 form together with the nitrogen atom to which R17 is attached and the carbon atoms of the benzene ring to which R22 and N—R17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• and/or
• R18 and R19 form with the nitrogen atom to which R18 is attached and the carbon atoms of the benzene ring to which R19 and N—R18 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• R15, R16, R19, R20, R21, R22, R23 and R24 are independently of each other selected from the group consisting of hydrogen, NR25R26, OR25, SR25, NR25—NR26R27, NR25—OR26, O—CO—R25, O—CO—OR25, O—CO—NR25R26, NR25—CO—R26, NR25—CO—OR26, NR25—CO—NR26R27, CO—R25, CO—OR25, CO—NR25R26, S—CO—R25, CO—SR25, CO—NR25—NR26R27, CO—NR25—OR26, CO—O—CO—R25, CO—O—CO—OR25, CO—O—CO—NR25R26, CO—NR25—CO—R26, CO—NR25—CO—OR26, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R25, R26 and R27 are independently of each other selected from hydrogen, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• A is a residue of formulae A.1, A.2, A.3, A.4, A.5, A.6 or A.7
• where
• # denotes the bond to the remaining compound of formula I
• R29 is a residue G, hydrogen, halogen, OR36, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R30, R31, R32 and R33 are independently of each other selected from a residue G, hydrogen, halogen, OR36, NO2, CN, COR′, COOR′, SO2R′ and SO3R′, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R′ is independently selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted alkyl having 1 to 10 carbon atoms, substituted alkyl having 1 to 10 carbon atoms including substituents, unsubstituted cycloalkyl having 5 to 7 carbon atoms, and substituted cycloalkyl having 5 to 10 carbon atoms including substituents, wherein in said alkyl or cycloalkyl groups one oxygen atom or two nonadjacent oxygen atoms may be inserted between respective C atoms;
• wherein optionally in (A.7) R30 and R31 together with the carbon atoms to which they are attached or R32 and R33 together with the carbon atoms to which they are attached form an unsubstituted or substituted 5-, 6- or 7-membered ring;
• with the proviso that at least one of the residues R29, R30, R31, R32, R33, R34 and R35 is a residue G,
• where
• R36 is unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combination thereof;
• Q is —S—, —C(R34)(R35)—, —O—;
• R34 and R35 are independently of each other selected from a residue G, hydrogen, halogen, OR36, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C90-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• G is selected from —R28—COOH, —R28—COO−Z+, —R28—CO(C═O)OH, —R28—CO(C═O)O−Z+, —R28—S(═O)2OH, —R28—S(═O)2O−Z+, —R2—O—S(═O)2OH, —R28—O—S(═O)2O−Z+, —R28—P(═O)(OH)2, —R28—P(═O)(O−Z+)2, —R28—P(═O)(OH)(O−Z+), —R28—O—P(═O)(OH)2, —R28—O—P(═O)(O−Z+)2, —R28—O—P(═O)(OH)(O−Z+), —R28—CO—NH—OH, —R28—S(═O)2NH—OH, —R28—NR14—S(═O)2OH and —R28—NR14—S(═O)2O−Z+;
• where
• R28 is a direct bond, C1-C20-alkylene, C2-C4-alkenylene or C6-C10-arylene;
• Z+ is an organic or inorganic cation equivalent;
• and
• Y− is an anion capable of absorbing electromagnetic radiation having a wavelength in the range of from 400 nm to 1000 nm.

A dye in a dye sensitized solar cell comprising a compound of formula (I)

• where
• n is 1, 2, 3, 4, 5 or 6;
• R1 and R2 are independently of each other selected from hydrogen, unsubstituted C1-C20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, substituted C1-C20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, unsubstituted C1-C20-cycloalkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, substituted C1-C20-cycloalkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, unsubstituted C6-C20-aryl, substituted C6-C20-aryl, unsubstituted C6-C20-heteroaryl, substituted C6-C20-heteroaryl;
• or
• R1 can additionally be a residue of formula D;
• each D is independently selected from the group consisting of residues of formulae D.1 and D.2
• where
• * denotes the bond to the remaining compound of formula (I);
• R17 and R18 are independently of each other selected from unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, where R14 is hydrogen, C1-C20-alkyl or C6-C10-aryl;
• or
• R17 and R18 form together with the nitrogen atom to which they are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• or
• R17 and R20 form together with the nitrogen atom to which R17 is attached and the carbon atoms of the benzene ring to which R20 and N—R17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• or
• R17 and R22 form together with the nitrogen atom to which R17 is attached and the carbon atoms of the benzene ring to which R22 and N—R17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• and/or
• R18 and R19 form with the nitrogen atom to which R18 is attached and the carbon atoms of the benzene ring to which R19 and N—R18 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• R15, R16, R19, R20, R21, R22, R23 and R24 are independently of each other selected from the group consisting of hydrogen, NR25R26, OR25, SR25, NR25—NR26R27, NR25—OR26, O—CO—R25, O—CO—OR25, O—CO—NR25R26, NR25—CO—R26, NR25—CO—OR26, NR25—CO—NR26R27, CO—R25, CO—OR25, CO—NR25R26, S—CO—R25, CO—SR25, CO—NR25—NR26R27, CO—NR25—OR26, CO—O—CO—R25, CO—O—CO—OR25, CO—O—CO—NR25R26, CO—NR25—CO—R26, CO—NR25—CO—OR26, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R25, R26 and R27 are independently of each other selected from hydrogen, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• A is a residue of formulae A.1, A.2, A.3, A.4, A.5, A.6 or A.7
• where
• # denotes the bond to the remaining compound of formula I
• R29 is a residue G, hydrogen, halogen, OR36, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R30, R31, R32 and R33 are independently of each other selected from a residue G, hydrogen, halogen, OR36, NO2, CN, COR′, COOR′, SO2R′ and SO3R′, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R′ is independently selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted alkyl having 1 to 10 carbon atoms, substituted alkyl having 1 to 10 carbon atoms including substituents, unsubstituted cycloalkyl having 5 to 7 carbon atoms, and substituted cycloalkyl having 5 to 10 carbon atoms including substituents, wherein in said alkyl or cycloalkyl groups one oxygen atom or two nonadjacent oxygen atoms may be inserted between respective C atoms;
• wherein optionally in (A.7) R30 and R31 together with the carbon atoms to which they are attached or R32 and R33 together with the carbon atoms to which they are attached form an unsubstituted or substituted 5-, 6- or 7-membered ring;
• with the proviso that at least one of the residues R29, R30, R31, R32, R33, R34 and R35 is a residue G,
• where
• R36 is unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combination thereof;
• Q is —S—, —C(R34)(R35)—, —O—;
• R34 and R35 are independently of each other selected from a residue G, hydrogen, halogen, OR36, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• G is selected from —R28—COOH, —R28—COO−Z+, —R28—CO(C═O)OH, —R28—CO(C═O)O−Z+, —R28—S(═O)2OH, —R28—S(═O)2O−Z+, —R2—O—S(═O)2OH, —R28—O—S(═O)2O−Z+, —R28—P(═O)(OH)2, —R28—P(═O)(O−Z+)2, —R28—P(═O)(OH)(O−Z+), —R28—O—P(═O)(OH)2, —R28—O—P(═O)(O−Z+)2, —R28—O—P(═O)(OH)(O−Z+), —R28—CO—NH—OH, —R28—S(═O)2NH—OH, —R28—NR14—S(═O)2OH and —R28—NR14—S(═O)2O−Z+;
• where
• R28 is a direct bond, C1-C20-alkylene, C2-C4-alkenylene or C6-C10-arylene;
• Z+ is an organic or inorganic cation equivalent;
• and
• Y− is an anion capable of absorbing electromagnetic radiation having a wavelength in the range of from 400 nm to 1000 nm.

A compound of formula (I)

• where
• n is 1, 2, 3, 4, 5 or 6;
• R1 and R2 are independently of each other selected from hydrogen, unsubstituted C1-C20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, substituted C1-C20-alkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, unsubstituted C1-C20-cycloalkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, substituted C1-C20-cycloalkyl wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, unsubstituted C6-C20-aryl, substituted C6-C20-aryl, unsubstituted C6-C20-heteroaryl, substituted C6-C20-heteroaryl;
• or
• R1 can additionally be a residue of formula D;
• each D is independently selected from the group consisting of residues of formulae D.1 and D.2
• where
• * denotes the bond to the remaining compound of formula (I);
• R17 and R18 are independently of each other selected from unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof, where R14 is hydrogen, C1-C20-alkyl or C6-C10-aryl;
• or
• R17 and R18 form together with the nitrogen atom to which they are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• or
• R17 and R20 form together with the nitrogen atom to which R17 is attached and the carbon atoms of the benzene ring to which R20 and N—R17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• or
• R17 and R22 form together with the nitrogen atom to which R17 is attached and the carbon atoms of the benzene ring to which R22 and N—R17 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• and/or
• R18 and R19 form with the nitrogen atom to which R18 is attached and the carbon atoms of the benzene ring to which R19 and N—R18 are attached an unsubstituted or substituted 5-, 6- or 7-membered ring;
• R15, R16, R19, R20, R21, R22, R23 and R24 are independently of each other selected from the group consisting of hydrogen, NR25R26, OR25, SR25, NR25—NR26R27, NR25—OR26, O—CO—R25, O—CO—OR25, O—CO—NR25R26, NR25—CO—R26, NR25—CO—OR26, NR25—CO—NR26R27, CO—R25, CO—OR25, CO—NR25R26, S—CO—R25, CO—SR25, CO—NR25—NR26R27, CO—NR25—OR26, CO—O—CO—R25, CO—O—CO—OR25, CO—O—CO—NR25R26, CO—NR25—CO—R26, CO—NR2′—CO—OR26, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R25, R26 and R27 are independently of each other selected from hydrogen, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C4-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl,
• wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• A is a residue of formulae A.1, A.2, A.3, A.4, A.5, A.6 or A.7
• where
• # denotes the bond to the remaining compound of formula I
• R29 is a residue G, hydrogen, halogen, OR36, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R30, R31, R32 and R33 are independently of each other selected from a residue G, hydrogen, halogen, OR36, NO2, CN, COR′, COOR′, SO2R′ and SO3R′, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• R′ is independently selected from the group consisting of unsubstituted aryl, substituted aryl, unsubstituted alkyl having 1 to 10 carbon atoms, substituted alkyl having 1 to 10 carbon atoms including substituents, unsubstituted cycloalkyl having 5 to 7 carbon atoms, and substituted cycloalkyl having 5 to 10 carbon atoms including substituents, wherein in said alkyl or cycloalkyl groups one oxygen atom or two nonadjacent oxygen atoms may be inserted between respective C atoms;
• wherein optionally in (A.7) R30 and R31 together with the carbon atoms to which they are attached or R32 and R33 together with the carbon atoms to which they are attached form an unsubstituted or substituted 5-, 6- or 7-membered ring;
• with the proviso that at least one of the residues R29, R30, R31, R32, R33, R34 and R35 is a residue G,
• where
• R36 is unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, wherein alkyl is uninterrupted or interrupted by O, S, CO, NR14 or combination thereof;
• Q is —S—, —C(R34)(R35)—, —O—;
• R34 and R35 are independently of each other selected from a residue G, hydrogen, halogen, OR36, unsubstituted or substituted C1-C20-alkyl, unsubstituted or substituted C2-C20-alkenyl, unsubstituted or substituted C2-C20-alkynyl, unsubstituted or substituted C7-C20-aralkyl, unsubstituted or substituted C8-C20-aralkenyl, unsubstituted or substituted C8-C20-aralkynyl, unsubstituted or substituted C6-C20-aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted heterocyclyl, unsubstituted or substituted C5-C20-cycloalkyl, unsubstituted or substituted C5-C20-cycloalkenyl and unsubstituted or substituted C6-C20-cycloalkynyl, wherein alkyl, alkenyl, alkynyl or the aliphatic moieties in aralkyl, aralkenyl or aralkynyl are uninterrupted or interrupted by O, S, CO, NR14 or combinations thereof;
• G is selected from —R28—COOH, —R28—COO−Z+, —R28—CO(C═O)OH, —R28—CO(C═O)O−Z+, —R28—S(═O)2OH, —R28—S(═O)2O−Z+, —R2—O—S(═O)2OH, —R28—O—S(═O)2O−Z+, —R28—P(═O)(OH)2, —R28—P(═O)(O−Z+)2, —R28—P(═O)(OH)(O−Z+), —R28—O—P(═O)(OH)2, —R28—O—P(═O)(O−Z+)2, —R28—O—P(═O)(OH)(O−Z+), —R28—CO—NH—OH, —R28—S(═O)2NH—OH, —R28—NR14—S(═O)2OH and —R28—NR14—S(═O)2O−Z+;
• where
• R28 is a direct bond, C1-C20-alkylene, C2-C4-alkenylene or C6-C10-arylene;
• Z+ is an organic or inorganic cation equivalent;
• and
• Y− is an anion capable of absorbing electromagnetic radiation having a wavelength in the range of from 400 nm to 1000 nm.